Dehydrogenation of paraffin hydrocarbons



' are normally gaseousincluding ethane, propane Patented July 5, 1938 Um'rso STAT-ES PATENT OFFICE p 2.12am

Hans Tropsch, Chicago, 111., assignor to Universal Oil Products Company, Chicago, Ill.,'a corporation of Delaware No Drawing. Application June so, 1934,

Serial No. 'zaassa I i 3 Claims. -(c1. 260-:170) This invention relates more particularly to the ingwhat materials will be most effective in prodehydrogenation of paraflin hydrocarbons which and the butanes.

In a more speciflc'sense the invention is concerned with a process-for converting these low boiling members of the paraflin series of hydrocarbons into their corresponding oleiins which contain two atoms ofhydrogen'less per molecule and consequently have one double bond between carbon atoms.

There is a large commercial production of gaseous parailin hydrocarbons. They occur in very I large quantities in natural gas, particularly those gases associated with the production of crude oil and commonly known as casing-head gases and this; supply is further augmented by the gases produced in cracking oils for the production of gasoline although this latter type of pyrolytically produced gas contains substantial quantities of olefins' as Well as parafflnic hydrocarbons.

The greater part of the paramn gas production is used merely for domestic and industrial iuel purposes and not as a source of hydrocarbon derivatives on account of its unreactlve character in comparison with their olefinic counterparts.

In one specific embodiment the present invention comprises ,the dehydrogenation of gaseousparafiin hydrocarbons at elevated temperatures in the presence of catalysts comprising magnesium oxide activated by chromium and/or zinc compounds.

In a preferred embodiment the catalyst consists of magnesium oxide activated or promoted by the presence of small amounts of zinc oxide and/or chromium oxides.

The field of catalysis is in general empirical as but few rules-have been evolved out of a large mass of experimental data. For each specific type of chemical reaction certain catalysts or groups of catalysts have been found to be of value. As an example, in sulphuric acid manufacture wherein sulphur dioxide is oxidized to sulphur trioxide, the noble metals platinum and palladium have been found to be effective catalysts and also vanadium oxides, although these substances are widely different chemically. -In thefield of hydrogenation the oxides and sulphides of metals of the 6th group of the periodic table including chromium, molybdenum and tungsten have been found to be of value, particularlyon account of their resistance to sulphur poisoning. These two instances are merely cited to show that in the held of. catalysis there is little chance. of predictmoting a given type of reaction.

In the presentinstance the catalyst mixtures which are preferred for selectively dehydrogenatthis purpose mixtures comprising major amounts of magnesium oxide and minor amounts of zinc and chromium compounds, particuarly their oxides, have been found to be particularly valuable and eflicient. While magnesium oxide alone is an eiiective dehydrogenating catalyst in the above sense, the tendency to carbon deposition is less- Y ened by the use of the present type of activators so that the dehydrogenatlng action is rendered more definite and effective.

-In making up catalyst composites of the preferred character and composition, the following is the simplest and generally the preferred procedure. Natural magnesite is calcined at temperatures of from 800 to 900 C. to produce a mixture containing a high percentage of magnesium oxide, the oxide is then ground to produce granules of relatively small mesh and these are given the requisite amounts of chromium and zinc compounds'by mixing them with aqueous solutions or suspensions of selected salts or salt mixtures. The magnesium oxide resulting from calcination has a high absorptive capacity for the activating materials and readily takes up the required percentages from aqueous solutions. To insure complete absorption of salts from the solutions and at, the same time a uniform distribution upon the magnesium oxide granules, the latter may be added to relatively fdilute solutions of salts and these may then be concentrated until a crit-. ical point is reached corresponding to complete removal of dissolved material. At this point the solvent may be removed by filte ng or pressing or evaporation by heat. Other alternative methods of preparing the preferred composite catalysts maybe employed. For

as, for example, sodium carbonate. this serving to nx the precipltatesupon thegranules or sium oxide. Usually the mixed solid particles are then ignited to produce a mixture of oxides. 5 When using solutions of zinc and chromium nitrates the mixtureof magnesium oxide granules and the solution may be evaporated to and further heated to decompose the nitrates and produce residual oxides. W Z

In regard to the proportions of the three components of the preferred catalysts, magnesium oxide is ordinariiy 'used in largest quantity and in some cases mixtures may be effectively employed which contain 90% by weight of magnesium oxide and 5% each of chromium and compounds. Very efl'ective dehydrogenating' catalysts for the present time of reactions are those containing approximately 90 toj95% of magnesium oxide and 5 to 10% of a mixture of zinc oxide and chromium oiddes.

In practicing the dehydrogenation of parai'flnic gases according to the ly proportioned mixture of used as a filler in a reaction the form of particles of aded size or small pellets and the gas to be dehydrogenated is passed through thecatalyst after being heated to the proper temperature, usually within the range of from 300 to 700 C. The catalyst tube may be heated exteriorly if desired to maintain the proper reaction temperature. The pressure employed may be atmospheric or slightly superatmospheric of the order of from 50 to 100 pounds per square inch, though any large amount of pressum has a tendency to depress the dehydrogenation reactions disproportionately to theffincrease in capdcity of the plant. i 'i'lhe exit gases from the tube or be passed through selective absorbents to com- 40 bine with or absorb theolefln or olefin mixture produced or theoleflns may be selectively polymerized by suitable catalysts, caused to alkylate other hydrocarbons such as aromatics or treated directly with chemical reagents to produce de- 5 sirable and commercially valuable derivatives. After the oleflns have been removed the residual gases may be recycled for further dehydrogenatlng treatment with or withoutreniova'l of hydrogen. e The present time of catalyst unusually selective in removing two hydrogen atoms from a paraffln' molecule to produce the corresponding olefin without furthering to any great degree undesirable side reactionsfnnd because of this shows an unusually long period of activity in service as will be shown in af later example. When, however,'theactieity begins to diminish it is readily regenerated by the simple expedient of oxidizing with air or other oxidizing gas at'a so moderately elevated temperature, usually within the range employed in the dehydrogenating re; actions." This 'oxidation efiectively jremoves traces of carbon deposits which contaminate the surface of the oxides and decrease their efilciency. It is characteristic of the present type or catalyst that it may be repeatedly regenerated without loss of porosity or catalyzing efliciency.

Numerous experimental data could be adduced magnepresent process a selectivethe three oxides is tube or chamber in chamber may to indicate the results obtainable by employing the present type of catalyst to dehydrogenate par= W ailins but the following single example issuflicient to show the general effectiveness of the preferred oxide mixture. 7 A catalyst was employed which consisted of 94% magnesium oxide, 3% chromium triexide and 3% zinc oxide, the mix having been made by impregnating the granular magnesium oxide with the nitrates of ehromium and zinc in the required proportions and then igniting at'a temperature oi approximately 500 C. V

Using small pellets of the above oxide mixture Qi made by moistening and compressing and later ldryinaisobutane was passed'through a treating tower containing the pellets as flller at atmospheric pressure and temperature of about 600 7 C., with a space velocity of from 40 to 50 per hour. The following table shows the nature of the results obtained by means of gas analyses taken at indieated times from the start of the run.

Composition of dehydrogenated eases Time alter start, hours 40 150 250 i-Bntylene, percent 2A. 5 23. 4 24. 5 24. 6 Other butylenes and propylene, percent. 6. 4 5. 3 5. 5 6. 0 Ethylene, percent 2. i 2. 2 4. 5 2.0 P as (mainly i-butane) cent.-- 35. 1 37. 2 35.5 38.5 Hydrogen, percent 3i. 9 31. 9 30. 0 29. 0

. From the above data it will be seen that the dehydrogenation corresponds closely to the calculated equilibrium mixture at 600 0., which should contain approximately'33% hydrogen, 33% butane and 33% butylenes. Substantially 50% of the original isobutanezwas converted into oleflns and hydrogen.

It is to be further observed that the catalytic activity is maintained substantiallyconstant for the period of the run of approximately 10 days? The foregoing specification'and example are sufllcient to show that the invention has intrinsic value when practiced in the art, but neither-is to be construed as imposing limitations upon the scope of the invention, as both are given f'or'illustrative purposes only;

I claim as my invention:

1. {L processrfor the dehydrogenation of gaseous p'arafljn hydrocarbons to produce olefin hydrocarbons whioh. comprises, subjecting the said gaseous paraflin hydrocarbons to an elevated teinperature in the presence of magnesium oxide, "chromium trioxide and zinc oxide.

2. A process for the treatment of gaseous paraflinic hydrocarbons to produce olefin hydrocarbons therefrom which' comprises, heating the said gaseous Daraitlnic hydrocarbons in the presence of a catalystecomprising approximately by weight of magnesium oxide and 5% each by weight'of chromium trioxide and zinc oxide.

3. A process for the dehydrogenation of gaseous parafllnic hydrocarbons to produce olefinic hydrocarbons therefrom which comprises, subjecting the said gaseous paraflinichydrocarbons while in heated condition to the action of a catalyst comprising'not less than 90% magnesium oxide and containing in addition chromium trioxide and zinc oxide.

HANS 'I'ROPSCE. 

